Aryl aryl-oxyalkylated sulfite esters



United States Patent 3 179 683 ARYL ARYL-OXYALKYLZATED SULFITE nsrnns Winchester L. Hubbard, Woodbridge, Allen E. Smith, Oxford, and Rupert A. Covey, Wolcott, Conn, assignors to United States Rubber Company, New York, N.Y., a

corporation of New Jersey No Drawing. Filed Aug. 20, 1962, Sci. No. 218,093 6 Claims. (Cl. 260-456) in which R and R are aromatic radicals, e.g. phenyl, or naphthyl, or a phenyl or a naphthyl (aryl) radical having one or more substituents in the aryl nucleus selected from the group consisting of alkyl having up to 9 carbon atoms, cycloalkyl, haloalkyl, alkoxy and halo; n is 2 to 10, and m is 1 to 10. Where m is greater than 1, the

repeating oxyalkyl groups may be the same or different.

Examples of R and R are phenyl, l-naphthyl, Q-naph-thyl, p-tolyl, o-tolyl, isopropylphenyl, ter-tfibutylphenyl, tert. amylphenyl, nonylphenyl, cyclohexylphenyl, chloromethylphenyl, methoxyphenyl, and haloaryl having up to halo radicals, e.g. bromophenyl, -2-chlor-ophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl. Exam ples of the -OC I-I group are ethyleneoxy, trimethyleneoxy, tetramethyleneoxy, propyleneoxy, 1,-2-di methylethyleneoxy.

The preparation of the chemicals of the invention may be carried out by reacting the selected phenol with the separately prepared chlorosulfinate of the selected glycol ether, which may be made by reacting the selected glycol ether with thionyl chloride. The glycol ether which is a glycol monoether may be made by reacting the selected phenol, with one to ten moles of the selected alkylene oxide per mole of the phenol. Such preparation is illustrated by the following reactions with the same symbols R, R and m as in the above general formula and for convenience using ethylene oxide (11:2) as the alkylene oxidez Reaction (1) above is a well known and smooth reaction. With one mole of alkylene oxide per mole of phenol, the result will be substantially a single compound containing one 'alkylene oxide unit. With two or 3,179,683 Patented Apr. 20, 1965 ture of products having varying numbers of alkylene oxide units is produced. lf a compound with a specific number of alkylene oxide units is desired, the mixture may be fractionated. In the present invention for insecticidal uses, it is satisfactory to have mixtures of compounds containing difi'erent numbers of alkylene oxide units from 1 tom. The following reaction of patent.- butyl phenol with propylene oxide is illustrative of the well known preparation of the starting glycol ethers according to reaction (1) above:

p-Tert.-butyl phenol (300 g., 2.0 moles.) and 4 g. so dium hydroxide were combined and the mixture heated to 150 C. Propylene oxide (279 ml., 232 g, 4.0 moles) was added during two hours maintaining the reaction tern- :pera'ture at l=5 0-l60 C. The mixture was cooled, the catalyst was neutralized with dilute hydrochloric acid, and the product taken up in benzene. The benzene was removed and the product heated to 90 C. (0.5 mm.) to remove the last traces of volatile materials. The crude reaction mixture weighed 509 g. (95.7% It was a mix- 1 ture of compounds having the structure more moles ofalkylene .oxide per mole :of pheno1,-a mixt wnmd-Qwcmenmon where m=1, 2, 3, 4, 5, etc. The mixture was distilled and the following fractions collected:

Percent m==1, B:P. l07 l-28 C. (1 mm.) 3-2 m=2, 13.1. 1-28'153 C. (-1 mm.) 47 m= 3, BJP. 163.1*84 C. (1 mm.) 14 Residue 7 Center cuts of these fractions yielded the pure compounds as follows? The preparation of the chlorosulfinates of the glycol ethers according to reaction (2) is carried. out at a torn perature of between 5 C. and 30 C., preferably near 0 C., and the yield of chlorosulfinate is nearly quantitative. An inert solvent such as benzene, xylene or solvent naphtha may be used. This is illustrated in Example I below. I

The preparation of the sulfite esters is carried out in the presence of an HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine, and in a solvent such as benzene, xylene or solvent naphtha. The reaction temperature is generally between l0 C. and 50 C., preferably near 0 C. This is illustrated in Example I below.

. Examples of the sulfite diesters of the present invention are:

p-Methoxyphenyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite i o'-Tolyl p-cyclohexylphenoxyisopropyl sulfite Phenyl p-toloxyoctyl sulfite l-naphthyl p-chloromethylphenoxyethyl sulfite.

l-naphthyl p-methoxyphenoxyethoxyethyl sulfite l-naphthyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite o-Tolyl -toloxyisopropyl sulfite o-Tolyl o-toloxyethyl sulfite o-Tolyl phenoxyisopropyl sulfite o-Tolyl p-isopropylphenoxyethyl sulfite o-Tolyl l-orthotoloxy-Z-butyl sulfite o-Tolyl p-isopropylphenoxyisopropyl sulfite m-Tolyl p-tert.-butylphenoxyisopropyl sulfite Example I illustrates the preparation of the compounds of the present invention.

EXAMPLE I Preparation of o-tolyl p-tert.-butylphen0xyisopropyl sulfite p-Tert.-butylphenoxyisopropyl chlorosulfinate was prepared as illustrated in reaction (2) above as follows: p-tert.-butylphenoxyisopropyl. alcohol or propylene glycol mono-p-tert.-butylphenyl ether (104 g., 0.5 mole) prepared according to reaction 1) as described above was dissolved in 150 ml. benzene and the solution was cooled to 0 C.- C. Thionyl chloride (45.4 ml., 74.4 g., 0.625 mole) was added dropwise during one hour, maintaining the reaction temperature below 5 C. The mixture was allowed to warm to room temperature and stand for hours. The benzene was evaporated under reduced pressure at room temperature and the residue was warmed to 35 C. (0.8 mm.) to remove the last traces of solvent. Yield, 141.3 g. (97.3%) of a pale yellow oil which was nearly odorless and relatively stable when stored in a refrigerator.

The o-tolyl p-tert.-butylphenoxyisopropyl sulfite was prepared as illustrated in reaction (3) above as follows: o-cresol (5.9 g., 0.055 mole), 4.1 ml. (4.0 g., 0.05 mole) pyridine and 30 ml. xylene were combined andthe solution cooled to 0 C.-5 C. A solution of 14.5 g. (0.05 mole) p-tert.-butylphenoxyisopropyl chlorosulfinate in 10 ml. xylene was added during min. keeping the reaction temperature below 5 C. The mixture was stirred for 1 hour and was washed twice with ml. portions of water. The mixture was then stirred for one hour with 50 ml. 2N NaOH. The two layers were separated and the xylene layer was washed several times with saturated salt solution until the washings were neutral to pH paper. The xylene was removed under reduced pressure and the residue heated to a pot temperature of 135 C. (0.7 mm.). The product was filtered through Dicalite (a diatomaceous earth filter-aid) giving 13.9 g. (77% yield) of a reddish yellow oil. Analysis.-Calculated for C H O S: C, 66.26%; H, 7.23%; S, 8.85%. Found: C, 67.44%; H, 7.68%; S, 8.13%.

Sulfur analyses of other chemicals of the present invention were:

Nonylphenyl p-tert.-butylphenoxyisopropyl sulfite. Calculated S, 6.75%. Foundi 6.77%.

p-Tert.-butylphenyl p-tert. amylphenoxyethyl sulfite. Calculated S, 7.92%. Found: 7.36%.

o-Tolyl' p-tert.-amylphenoxyethyl sulfite. 8.85%. Found: 8.31%.

oTolylo-to1oxyisopropyl sulfite. Calculated S, 10.01%. Found: 9.80%.

o-Tolyl o-toloxyethyl sulfite. Foundi 10.29%.

Phenyl p-isopropylphenoxyethyl sulfite. Calculated S,

9.99%. Found: 9.65%.

Calculated S,

Calculated S, 11.05

o-Tolyl phenoxyisopropyl sulfite. Calculated S, 10.48%. Found: 9.91%.

o-Tolyl p-isopropylphenoxyethyl sulfite. Calculated S, 9.59%. Found: 9.08%.

o-Tolyl l-orthotoloxy-Z-butyl sulfite. 9.59%. Found: 9.17%.

o-Tolyl p-isopropylphenoxyisopropyl sulfite. lated S, 9.20%. Found: 8.51%.

o-Tolyl l-paraisopropylphenoxy-Z-butyl sulfite. Calculated S, 8.85%. Found: 8.04%.

o-Tolyl 1-paratertiaryamylphenoxy-Z-butyl sulfite. Calculated S, 8.20%. Found: 7.38%.

o-Tolyl 3-paratertiarybutylphenoxy-Z-butyl sulfite. Calculated S, 8.52%. Found: 8.37%.

o-Tolyl 1-paratertiarybutylphenoxy-Z-amyl sulfite. Calculated S, 8.33%. Found: 7.55%.

EXAMPLE II This example illustrates the insecticidal activity of the chemicals of the present invention in tests against the larvae of Aedesaegypti (L.) mosquitoes. Fourth instar larvae were used. These larvae normally reach this stage in 5 days at F. after hatching.

To 10 mgs. of each. chemical to be tested was added 1 ml. of acetone and ml. of water to give a concentration of 100 parts per million (p.p.m.).

Twenty-five ml. aliquots, replicated once, of each chemical to be tested at concentrations of 100 p.p.m. and

Calcu of checks without the chemical and of plain water checks were placed in test tubes and from 5 to 25 larvae were added. The tubes were held at 70 F. in darkness for 72 hours. At the end of this period the live and dead larvae were counted and the percent mortality calculated. All the larvae were alive in the checks (0% mortality). The percent mortality of the larvae treated with the chemicals of the present invention is shown in the following table.

Chemical: 7 Percent mortality oTolyl p-tert.-butylphenoxyisopropyl sulfite 100 Nonylphenylp-tert.-butylphenoxyisopropylsulfite 47 EXAMPLE III This example illustrates the effectiveness of the chemicals of the present invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" baskets under greenhouse conditions at 70 F.-75 F.

were used. Three plants for a total of six leaves were.

in each basket for each test. The tests on the chemicals and checks were replicated once. Aqueous suspensions of the chemicals were prepared by adding to 0.2 gram of the chemical one drop.(0.03 gram) of a commercial surface-active dispersing agent (isooctylphenyl polyethoxy ethanol) and 1 ml. of acetone, washing into 200 ml. of water, agitating to form a dispersion and diluting with water to the desired concentrations of 1000 p.p.m.'and 200 ppm.

The plants were sprayed with the dispersions of the chemicals at the various concentration and the check plants were sprayed with aqueous solutions containing.

ing bean leaflets heavily infested with two-spotted adult mites, Tetrr mychu's telarius L. within the border of the Y adhesive preparation on the leaves of the plants under test. A count of the number of mites transferred was made the same day. The counts ranged fr'om 30 to 300 mites on the six leaves. The plants were kept in the greenhouse for another four days. A final count of the 7 Calculated S,

5 number of living mites remaining on the leaves was then made. The percent control is found by using the formula:

Percent control: 100(1 Original count Percent Control at- Chemicals 1,000 200 p.p.m. p.p.m.

o-Tolyl p-tert.-butylphenoxyisopropyl sulfite 100 92 Nonylphenyl p-tert.-butylphenoxyisopropyl sulfite 59 p-Tert.-bntylphenyl p-tert.-amylphenoxyethyl snlfim 99 82 o-Tolyl p-tert.-amylphenoxyethyl sulfite. 100 95 o-Tolyl o-tolyloxyisopropyl sulfitc 100 79 o-Tolyl o-tolyloxyethyl sulfite 96 96 Phenyl pisopropylphenxyethy1 sulfite. 94 71 o-Tolyl phenoxyisopropyl sulfite 80 75 o-Tolyl p-isopropylphenoxyethyl sulfite 99 66 o-Tolyl l-orthotoloxy-Z-butyl sulfite 99 95 o-Tolyl p-isopropylphenoxyisopropyl sulfite. 99 93 m-Tolyl p-tcrt.-butylphenoxyisopropyl sulfi 91 90 o-Tolyl 1-paraisopropylphenoxy-2-butyl sulfite 97 76 o-Tolyl 1-paratertiarybutylphenoxy-2-butyl sulfite. 100 99 o-Iolyl l-paratertiaryamylphenoxy-2butyl sulfite. 98 97 o-Tolyl 3paratertiarybutylphenoxy-2-buty1 sulfite, 100 97 o-Tolyl 1-paratertiarybutylphenoxy-2-amylsulfite 100 95 o-Tolyl p-tcrt.-butylphenoxyisopropoxyisopropyl EXAMPLE IV This example also illustrates the eifectiveness of the chemicals of the present invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" baskets under greenhouse conditions at 70 F.75 F. were used. Two plants for a total of four leaves were in each basket for each test. These tests on the chemicals were replicated once.

The untreated leaves were ringed with adhesive and 40-50 mites were transferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of the leaves with aqueous solutions of the chemicals at concentrations of 200' p.p.m., 100 ppm. and 5 0 ppm. prepared as in Example III.

The plants were allowed to dry and a count of the mites was made. The plants were kept in the greenhouse for three days. A final count of the living mites remaining on the leaves was then made. The percent control is found by the formula used in Example HI.

The control of mites by the chemicals of the present invention is shown in the following table:

The chemicals of the present invention may be applied in various manners for the control of insects. They may be applied to loci to be protected against insects as dusts when admixed with or adsorbed on powdered solid carriers, such as the various mineral silicates, e.g. mica, talc, pyrophyllite and clays, or as liquids or sprays when in a liquid carrier, as in solution in a suitable solvent, such as acetone, benzene or kerosene, or dispersed in a suitable non-solvent medium, for example, water. In protecting plants (the term including plant parts) which are subject to attack by insects, the chemicals of the present invention are preferably applied as aqueous emu sions containing a surface-active dispersing agent, which may be an anionic, non-ionic or cationic surface-active agent. Such surface-active agents are well known and reference is made to US. Patent No. 2,547,724, columns 3 and 4 for detailed examples of the same. The chemicals of the invention may be mixed with such surfaceactive dispersing agents, with or without an organic solvent as insecticidal concentrates for subsequent addition of water to make aqueous suspensions of the chemicals of the desired concentration. The chemicals of the invention may be admixed with powdered solid carriers, such as mineral silicates together with a surface-active dispersing agent so that a wettable powder may be obtained, which may be applied directly to loci to be protected against insects, or which may be shaken up with water to form a suspension of the chemical (and powdered solid carrier) in water for application in that form. The chemicals of the present invention may be applied to loci to be protected against insects by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the aerosol carrier which is liquid under pressure but which is a gas at ordinary temperature (e.g., 20 C.) and atmospheric pressure, or the aerosol solution may be prepared by first dissolving the chemical in a less volatile solvent and then admixing such solution with the highly volatile liquid aerosol carrier. The chemicals may be used admixed with carriers that are active of themselves, for example, other insecticides, fungicides or bactericides.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A chemical represented by the general formula in which R and R are selected from the group consisting of phenyl, naphthyl, phenyl and naphthyl having substituents consisting of up to 5 halo radicals selected from the class consisting of bromo and chloro, and mono-substituted phenyl and naphthyl having the substituent selected from the group consisting of alkyls having up to 9 carbon atoms, cyclohexyl, chloromethyl and methoxy, n is 2 to 10, and m is 1 to 10.

2. o-Tolyl p-tert.rbutylphenoxyisopropyl sulfite.

3. o-Tolyl p-tert.-amylphenoxyethyl sulfite.

4. p-Tert.-butylphenyl p-tert.-amylphenoxyethyl sulfite.

5. o-Tolyl p-tert.-butylphenoxyisopropoxyisopropyl sulfite.

6. p Tert.-butylphenyl p-tert.-butylphenoxyisopropyl sulfite.

References Cited by the Examiner UNITED STATES PATENTS 2,465,391 3/49 Myles 260456 2,820,808 1/58 Harris et a1. 260456 2,867,564 1/59 Richter 260456 X 2,901,338 8/59 Richter 260456 X 2,905,587 9/59 Dowling 167--30 CHARLES B. PARKER, Primary Examiner.

J. S. LEVITT, JOSEPH P. BRUST, Examiners. 

1. A CHEMICAL REPRESENTED BY THE GENERAL FORMULA 